Energy intramolecular

Oxtoby D W and Rice S A 1976 Nonlinear resonance and stochasticity in intramolecular energy exchanged. Chem. Phys. 65 1676-83... 

Shirts R B and Reinhardt W P 1982 Approximate constants of motion for classically chaotic vibrational dynamics vague tori, semiclassical quantization, and classical intramolecular energy flow J. Cham. Phys. 77 5204-17... 

Rynbrandt J D and Rabinovitch B S 1971 Direct demonstration of nonrandomization of internal energy in reacting molecules. Rate of intramolecular energy relaxation J. Chem. Phys. 54 2275-6... 

In this chapter we shall first outline the basic concepts of the various mechanisms for energy redistribution, followed by a very brief overview of collisional intennoleciilar energy transfer in chemical reaction systems. The main part of this chapter deals with true intramolecular energy transfer in polyatomic molecules, which is a topic of particular current importance. Stress is placed on basic ideas and concepts. It is not the aim of this chapter to review in detail the vast literature on this topic we refer to some of the key reviews and books [U, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, and 32] and the literature cited therein. These cover a variety of aspects of tire topic and fiirther, more detailed references will be given tliroiighoiit this review. We should mention here the energy transfer processes, which are of fiindamental importance but are beyond the scope of this review, such as electronic energy transfer by mechanisms of the Forster type [33, 34] and related processes. 

A 3.13.2 BASIC CONCEPTS FOR INTER- AND INTRAMOLECULAR ENERGY TRANSFER... 

Figure A3.13.1 illustrates our general understanding of intramolecular energy redistribution in isolated molecules and shows how these processes are related to intemiolecular processes, which may follow any of the mechanisms discussed in the previous section. The horizontal bars represent levels of nearly degenerate states of an isolated molecule.

Figure A3.13.1. Schematic energy level diagram and relationship between mtemiolecular (collisional or radiative) and intramolecular energy transfer between states of isolated molecules. The fat horizontal bars indicate diin energy shells of nearly degenerate states.

A 3.13.4 INTRAMOLECULAR ENERGY TRANSFER STUDIES IN POLYATOMIC MOLECULES... 

A 3.13.6 STATISTICAL MECHANICAL MASTER EQUATION TREATMENT OF INTRAMOLECULAR ENERGY REDISTRIBUTION IN REACTIVE MOLECULES... 

Marcus R A 1983 On the theory of intramolecular energy transfer Faraday Discuss. Chem. Soc. 75 103-15... 

For the case of intramolecular energy transfer from excited vibrational states, a mixed quantum-classical treatment was given by Gerber et al. already in 1982 [101]. These authors used a time-dependent self-consistent field (TDSCF) approximation. In the classical limit of TDSCF averages over wave functions are replaced by averages over bundles of trajectories, each obtained by SCF methods. 

Gerber, R.B., Buch, V., Ratner, M.A. Time-dependent self-consistent field approximation for intramolecular energy transfer. I. Formulation and application to dissociation of van der Waals molecules. J. Chem. Phys. 77 (1982) 3022-3030. 

Influence of the Fiber. In order for a dye to move from the aqueous dyebath to the fiber phase the combination of dye and fiber must be at a lower energy level than dye and water. This in turn implies that there is a more efficient, lower energy sharing of electrons or intramolecular energy forces, and there are a number of mechanisms that allow this to happen. 

For elimination of intramolecular energy losses, we have synthesized ligands with high hydrophobisity - perfluoro-P-diketones R -CO-CH -CO-R, (R = CgF j or CgF R = phenyl or a-thienyl), that without second ligand eliminate completely water molecules from the inner coordination sphere. These ligands we have used in analysis at determination of Sm, Eu, Nd, Yb microamounts in high-purity lanthanide and yttrium oxides. 

Unfortunately, there is no consensus on the measure for defining the energy of an explosion of a pressure vessel. Erode (1959) proposed to define the explosion energy simply as the energy, ex,Br> must be employed to pressurize the initial volume from ambient pressure to the initial pressure, that is, the increase in internal energy between the two states. The internal energy 1/ of a system is the sum of the kinetic, potential, and intramolecular energies of all the molecules in the system. For an ideal gas it is... 

Hydrogen molecule, carbon oxide intramolecular energy, 110 clathrates, 12, 20 correlated wave function, 300... 

Extrusion or elimination of small stable species such as CO2 Intramolecular energy transfer Quenching involving translational or vibrational excitation of another molecule... 

The dependence on the nuclear positions is indicated by r and the dependence on the Drude positions is indicated by d. In Eq. (9-25) Ubond (r) is the intramolecular energy contribution from, typically, the bond lengths, valence angles, and dihedral angles, Ulj (r) is a Lennard-Jones 6-12 nonpolar contribution, Ueiect (r, d) represents all Coulombic interactions, atom-atom, atom-Drude, and Drude-Drude, and Useif (d) represents the atom-Drude harmonic bonds. The term Usey (d) arises from the harmonic spring separating the two charges and has the simple expression... 

Irradiation of solutions containing equimolar amounts of n = 1-4 and /ra/is-j9-methylstyrene as a quencher at concentrations comparable to those of the experiments reported in Table 6.6 indicated that intermolecular energy transfer cannot compete with intramolecular energy transfer under these conditions. 

Flexible force field models require 30 or more beads in Cartesian path integral descriptions to obtain converged intramolecular energies. Rigid water models require only about five beads due to the weaker intermolecular quantum effects. 

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